Process for the extraction of hops

ABSTRACT

Process for extracting from hops the essential brewing ingredients thereof, viz., neutral substances, bitter substances and tannin, which process comprises subjecting a primary extract solution of hops, e.g., in alcohol or hydrocarbon solvents, said solution containing as ingredients the neutral substances, bitter substances and tannin, to a first liquid-liquid extraction, wherein either (i) the tannins or (ii) the neutral substances are separated off, leaving a solution of (i) neutral and bitter substances or (ii) tannins and bitter substances, and subjecting the latter solution to a second liquid-liquid extraction to separate said solution into its components; the first extractant is desirably an aliphatic, cycloaliphatic or aromatic hydrocarbon when the primary extract solvent is an alcohol or aqueousalcoholic solution, to result in extraction of the neutral and bitter substances in a hydrocarbon phase and leaving of the tannin in the alcoholic phase, whereafter the neutral and bitter substances are separated from each other by treating the extract with a second extractant, desirably aliphatic alcohol containing water.

United States Patent 1 Bauer et al.

[ PROCESS FOR THE EXTRACTION OF HOPS [75] Inventors: Kurt Bauer;l-lelmut Findeiss; Alfred Krempel, all of Holzminden, Germany [73]Assignee: Haarmann & Reimer GmbI-l,

Holzminden, Germany {22] Filed: Sept. 6, 1973 [21] Appl. No.: 394,899

Primary Examiner-A. Louis Monacell Assistant Examiner-R. B. PenlandAttorney, Agent, or FirmBurgess, Dinklage & Sprung June 24, 1975 [57]ABSTRACT Process for extracting from hops the essential brewingingredients thereof, viz., neutral substances, bitter substances andtannin, which process comprises subjecting a primary extract solution ofhops, e.g., in alcohol or hydrocarbon solvents, said solution containingas ingredients the neutral substances, bitter substances and tannin, toa first liquid-liquid extraction, wherein either (i) the tannins or (ii)the neutral substances are separated off, leaving a solution of (i)neutral and bitter substances or (ii) tannins and bitter substances, andsubjecting the latter solution to a second liquidliquid extraction toseparate said solution into its components; the first extractant isdesirably an aliphatic, cycloaliphatic or aromatic hydrocarbon when theprimary extract solvent is an alcohol or aqueousalcoholic solution, toresult in extraction of the neutral and bitter substances in ahydrocarbon phase and leaving of the tannin in the alcoholic phase,whereafter the neutral and bitter substances are separated from eachother by treating the extract with a second extractant, desirablyaliphatic alcohol containing water.

33 Claims, 3 Drawing Figures PATENTEDJUN 24 I975 FIG. Z.

1 D IIIM. E W 6 J M 5 C l 2 8 '19 a E 7 6 A 4 FIG. 3.

PROCESS FOR THE EXTRACTION OF HOPS This invention relates to a processfor extracting hops. Specifically, the present process extracts theneutral substances, bitter substances and tannins from hops as separatefractions.

Processes for producing hop extracts are known (Steiner Hopfen GmbH,Hopfen und Hopfenveredlungsprodukte, Oelde 1907, pages 414 421). In thepast, however, it has not been possible economically to recover theingredients present in hops as three separate extracts containing,respectively, the neutral substances, bitter substances and tanninsessential for brewing by processes yielding extracts which could safelybe used from the physiological point of view.

Neutral substances are the group of substances which influence thetypical odor and flavor of beer made from hops and which essentiallycontain the essential oils present in hops. Compounds belonging to thisgroup are essentially terpenes and sesquiterpenes such as, for example,humulene, B-caryophyllene farnesene, mycrene, and also oxy compoundssuch as, for example, Z-undecanone, geranylacetate, methyldec-4-enoateand methyldeca-4,6-dienoate. Neutral substances also include the groupof so-called unidentified soft resins" whose structure has not yet beenclarified (Monatschrift fur Brauerei 22, page 209, (1969)).

Bitter substances are the group of substances which provide thecharacteristically pleasant bitterness of beer and which consistessentially of humulone, cohumulone, adhumulone lupulones, colupuloneand adlupolone, and of the oxidative degradation products of thesesubstances.

Tannins are the group of substances which consist essentially oftannins, flavonoids and catechins (M. Dadic et al. J. Inst. Brew 76,267-280 (1970)).

A process for separating from hops the ingredients essential for brewinghas not been found, and the instant process yields physiologicallyacceptable extracts and is not subject to the drawbacks of priorprocesses.

Essentially, the process of the invention comprises subjecting ahop-extract solution containing neutral substances, bitter substancesand tannins, referred to hereinafter as the primary extract solution, toat least two successive liquid-liquid extractions to recover the neutralsubstances, the bitter substances and the tannins, by separating either(i) the tannins or (ii) the neutral substances from the primary-extractsolution in the first extraction stage and subjecting the remainingextract solution of (i) neutral and bitter substances or (ii') tanninsand bitter substances left after the first extraction stage to thesecond extraction stage for separation into its components.

The invention can be described in conjunction with the accompanyingdrawings, wherein:

FIG. 1 is a flow chart showing combining extraction stage A and B;

FIG. 2 is a flow chart showing combining extraction stages C and D;

FIG. 3 is a flow diagram of a typical extraction sequence.

The process according to the invention can be carried out, for example,by subjecting the primary extract solution to two successiveliquid-liquid extractions, the neutral and bitter substances beingseparated off from the tannins in an extraction stage A and the neutralsubstances and bitter substances being separated from each other in anextraction stage B.

In this case, the extractant 1 used for the extraction stage A isadapted in its polarity to the solvent composition of the primaryextract solution in such a way that the bitter substances and neutralsubstances are almost completely separated from the tannins in theextraction stage A, whilst the extractant 2 used for the extractionstage B is adapted in its polarity to the solvent composition of thesolution of bitter and neutral substances left after extraction stage A,in such a way that the neutral substances and the bitter substances arealmost completely separated from each other in the extraction stage B.

For the process according to the invention, it has proved to beadvantageous for example to use an alcoholic or alcoholic-aqueoussolution, preferably a mixture of a lower aliphatic alcohol with water,as the primary extract solution. It has also proved to be advantageousin some cases to use a halogenated hydrocarbon with from 1 to 3 carbonatoms and with up to 3 halogen atoms, preferably chlorine atoms, orbenzene or an alkyl benzene with a total of up to 8 carbon atoms, as thesolvent in the primary extract solution. It is preferred to use primaryextracts containing alcohol or an alcohol-water mixture, methylenechloride or benzene as solvent. Methanol and ethanol or mixtures ofthese alcohols with water are particularly preferred.

For example, in cases where alcoholic or alcoholicaqueous primaryextract solutions are used, it is possible to employ as extractant 1 forextraction stage A an aliphatic hydrocarbon with from 5 to 10 carbonatoms and/or a cycloaliphatic hydrocarbon with from 5 to 8 carbon atomsand/or an aromatic hydrocarbon such as benzene or an alkyl-substitutedbenzene derivative, in which case the neutral and bitter substances areextracted into the hydrocarbon phase whilst the tannins remain in thealcoholic-aqueous phase. Thereafter, the extract from extraction stage Ais subjected in accordance with the invention to the extraction stage B,for which a mixture of a lower aliphatic alcohol with water, forexample, can be used as the extractant 2, the bitter substances beingextracted into the alcoholic-aqueous phase and the neutral substancesremaining in the hydrocarbon phase.

In this embodiment, the chosen polarity of the hydrocarbons orhalogenated hydrocarbon phase is chosen to be sufficiently high inrelation to that of the alcoholicaqueous phase for extraction stage A sothat the neutral and bitter substances remain in the hydrocarbon orhalogenated hydrocarbon phase, whilst for extraction stage B thepolarity is reduced in relation to extraction stage A to such an extentthat the bitter substances are extracted from the hydrocarbon orhalogenated hydrocarbon phase in extraction stage B.

Instead of using hydrocarbons as extractants for extraction stage A, itis possible to employ halogenated hydrocarbons with l to 3 hydrocarbonatoms and up to 3 halogen atoms, preferably methylene chloride orchloroform. The extraction stage A proceeds in exactly analogous mannerwith a halogenated hydrocarbon extract forming which contains theneutral and bitter substances and which is extracted with mixtures oflower aliphatic alcohols and water, preferably with aqueous methanol,for the purpose of further separation in extraction stage B.

In cases where primary extract solutions in benzene or alkyl benzenes orin halogenated hydrocarbons are used, aliphatic alochols having from Ito 3 carbon atoms or mixtures thereof with water, preferably methanol orethanol and, with particular preference, methanol are correspondinglyused for extraction stage A, the tannins being extracted into thealcoholic or alcoholicaqueous phase and the neutral and bittersubstances remaining in the hydrocarbon or halogenated hydrocarbonphase. The raftinate containing neutral and bitter substances resultingfrom extraction stage A is then subjected to the extraction stage B.Stage A is then extracted according to the process of the invention inextraction stage B with mixtures of lower aliphatic alcohols and water;in cases where a halogenated hydrocarbon raftinate is present aqueousmethanol is preferably used as an extractant for extraction stage B.

The polarity of the hydrocarbon or halogenated hydrocarbon phase inrelation to the alcoholic-aqueous phase may be influenced on the onehand by varying the water content of the alcoholic-aqueous phase and onthe other hand by the particular alcohol chosen. For example, thepolarity of the alcoholic-aqueous phase increases with increasing watercontent and when the alcohol varies in the order propanol, ethanol,methanol, and also the polarity is affected by varying the solventcomposition of the hydrocarbon phase, for example by varying thecycloaliphatic hydrocarbon content or, in particular, the benzenehydrocarbon content. For example, the polarity of the hydrocarbon phasebecomes greater with increasing cycloaliphatic content and, inparticular, aromatic hydrocarbon content.

Instead of changing the polarity of the extractant 2 used for theextraction stage B, it is also possible, with the same solvent systemsin extraction stages A and B, to reduce the ratio by volume of theextract from extraction stage A to the extractant 2 in relation to thecorresponding volume ratio applied in extraction stage A, to such anextent that almost complete separation of the neutral substances andbitter substances is obtained in extraction stage B. In general, it hasproved to be particularly advantageous to reduce this volume ratio inextraction stage B to at least about half, preferably to at least onethird, of the corresponding value in extraction stage A.

Furthermore, the process according to the invention can be carried outby initially separating the neutral substances from the bittersubstances and tannins in the primary extract solution in a firstextraction stage C and separating the tannins from the bitter substancesin a second extraction stage D.

To this end, the extractant 3 used for the extraction stage C can beadapted in its polarity to the solvent composition of the primaryextract in such a way that the neutral substances are almost completelyseparated from the tannins and bitter substances in the extraction stageC, and furthermore, the extractant 4 used for the subsequent extractionstage D can be adapted in its polarity to the solvent composition of thesolution of bitter substances and tannins left after extraction stage Cin such a way that almost complete separation of the tannins and bittersubstances is obtained in extraction stage D.

For example, it has proved to be advantageous, where analcoholic-aqueous primary extract solution is used, to employ analiphatic hydrocarbon having from 5 to carbon atoms and/or acycloaliphatic hydrocarbon having from 5 to 8 carbon atoms and/or anaromatic hydrocarbon such as benzene or an alkylsubstituted benzenederivative, as extractant 3 for extraction stage C, in which case theneutral substances are extracted into the hydrocarbon phase whilst thebitter substances'and tannins remain in the alcoholicaqueous phase. Thealcoholic-aqueous phase left after extraction stage C is then subjectedin accordance with the invention to extraction stage D, in which analiphatic hydrocarbon having from 5 to 10 carbon atoms and/or acycloaliphatic hydrocarbon having from 5 to 8 carbon atoms and/or anaromatic hydrocarbon such as benzene or an alkyl-substituted benzenederivative can be used as extractant 4, the bitter substances beingextracted into the hydrocarbon phase and the tannins remaining in thealcoholic-aqueous phase.

In these embodiments, the polarity of the hydrocarbon or halogenatedhydrocarbon phase is chosen to be sufficiently high in relation to thatof the alcoholicaqueous phase for extraction stage C so that only theneutral substances are extracted from the alcoholicaqueous phase andremain in the hydrocarbon phase in extraction stage C, and furthermorethe polarity is increased for extraction stage D to such an extent thatthe bitter substances are extracted from the alcoholicaqueous phase inthis stage. The polarity of the hydrocarbon or halogenated hydrocarbonphase in relation to the alcoholic-aqueous phase can be controlled inthe same way as in extraction stages A and B.

In cases where primary extract solutions in benzene or alkyl benzenesare used, aliphatic alcohols having from 1 to 3 carbon atoms or mixturesthereof with water, preferably methanol or ethanol and, with particularpreference, methanol, are used as extractants for extraction stage C inwhich the bitter substances and tannins are extracted into the alcoholicor alcoholicaqueous phase whilst the neutral substances remain in thehydrocarbon phase. The raffinate containing tannins and bittersubstances from extraction stage C is then subjected to extraction stageD in accordance with the invention.

In the cases wherein primary extract solutions in halogenatedhydrocarbons are used, methanol or mixtures of methanol with water areused as extractants for extraction stage C, in which case the bittersubstances and tannins are extracted into the alcoholic oralcoholic-aqueous phase whilst the neutral substances remain in thehalogenated hydrocarbon phase.

The raffinate containing tannins and bitter substances from extractionstage C is then subjected to extraction stage D is accordance with theinvention.

The polarity of the hydrocarbon or halogenated hydrocarbon phase inrelation to the alcoholic phase can be influenced in the same way as inthe extraction stages A and B.

Instead of changing the polarity of the extractant 4 used for extractionstage D, it is also possible, with the same solvent system in extractionstages C and D, to increase the volume ratio of the extractant 4 to theextract of extraction stage C with respect to the corresponding volumeratio applied in extraction stage C to such an extent that almostcomplete separation of the bitter substances and tannins is obtained inextraction stage D. In general, it hasproved to be particularlyadvantageous to increase this volume ratio to approximately 5 times andpreferably to 20 times the corresponding value in extraction stage C.

The primary extract solution is best prepared by extracting hops withlower aliphatic alcohols, especially "th methanol, ethanol, propanol orisopropanol. The

primary extract can also be prepared by extracting hops with halogenatedhydrocarbons containing from 1 to 3 carbon atoms and up to 3 halogenatoms, preferably chlorine atoms, and also with benzene or alkylbenzenes containing a total of up to 8 carbon atoms. The following arementioned as examples of halogenated hydrocarbons: methylene chloride,chloroform, 1,1-dichloroethane, 1,2-dichloroethane and lchloropropane,preferably methylene chloride, whilst toluene, xylene and ethylbenzeneare mentioned as examples of alkyl benzenes. Methanol or ethanol ispreferably used as the extractant for preparing the primary extractsolution. Extraction is carried out in a conventional manner either byorthodox extraction (cf. Steiner Hopfen GmbI-I, Hopfen undHopfenveredlungsprodukte, Oelde 1970, pages 414 421 or, for example, inaccordance with the carousel extraction principle, (cf. ChemilterZeitung 94, (1970), pages 56 62).

Preparation of the primary extract solution for the process according tothe invention can be carried out, for example, with standard commercialdried raw hops as starting material. I-Iop powder, concentrated hoppowder or lupulin, and also water-containing fresh hops, can of coursealso be processed accordingly as starting materials.

Commercial hop extracts containing neutral substances, bitter substancesand tannins can also be separated by the process according to theinvention. In this case, the commercial extract is taken up in alcohol,hydrocarbons or halogenated hydrocarbons as solvents before separationin accordance with the invention and the resulting solution is used asthe primary extract solution.

The process according to the invention can be carried out in manydifferent ways owing to the large number of possible variations in thesolvent systems, in the volume ratios of extractant to the phase to beextracted and in the design of the extractors.

The following are mentioned as examples of the aliphatic hydrocarbonswhich can be used as extractants 1, 3 and 4: pentane, hexane, heptane,octane, nonane, decane, and the isomers of these compounds. It is, ofcourse, also possible to use mixtures of these compounds, for example afraction of aliphatic hydrocarbons boiling at a temperature in the rangeof from about 34 to C (pentane fraction), in the range of from about 65to C (hexane fraction), in the range of from about to C (heptanefraction), in the range of from about to C (octane fraction), in therange of from about to C (nonane fraction) or in the range of from aboutto C (decane fraction). It is preferred to use hexane, heptane or octaneor the corresponding hexane, heptane or octane fractions.

The following are mentioned as examples of the cycloaliphatichydrocarbons which can be used as extractants l, 3 and 4: cyclopentane,cyclohexane,cycloheptane, cyclooctane, and derivatives of thesecompounds substituted by lower alkyl groups. It is preferred to usecyclopentane and cyclohexane.

Benzene, optionally substituted once or several times by methyl, ethyl,propyl or isopropyl groups, is mentioned as one example of the aromatichydrocarbons which can be used as extractants l, 3 and 4. Toluene,

ethylbenzene and xylene are mentioned as preferred substituted benzenederivatives.

Methanol, ethanol, propanol and isopropanol are examples of the loweraliphatic alcohols which can be used as extractant 2. It is preferred touse methanol or ethanol.

Methylene chloride is mentioned as one example of the halogenatedhydrocarbons which can be used in extractants l, 3 and 4. g

It is preferred to use an alcoholic-aqueous and, with particularpreference, a methanolicor ethanolicaqueous primary extract solution forextraction stages A and C of the process according to the invention. Thewater content of this primary extract solution is adjusted to a value offrom about 5 to 70% by volume and preferably to from about 5 to 40% byvolume and, with particular preference, to from about 5 to 30% byvolume.

Extraction stage A is best carried out by extracting thealcoholic-aqueous primary extract solution with an extractant 1consisting of a mixture of aliphatic hydrocarbons with cycloaliphatichydrocarbons or with aromatic hydrocarbons. It is preferred to usemixtures comprising aromatic hydrocarbons, benzene, toluene or xylenepreferably being used as the aromatic hydrocarbon component.

It has proved to be advantageous, for example for extraction stage A, toadjust the water content of the alcoholic-aqueous phase to between about10 and 40% by volume, and the aromatic and cycloaliphatic hydrocarboncontent of extractant 1 to preferably between about 10 and 60% byvolume. For example, where the alcoholic primary extract solution has awater content of about 10% by volume, it is possible to use asextractant 1 a mixture of hydrocarbons, the aromatic hydrocarbon contentof which preferably amounts to between about 20 and 60% by volume, and,where it has a water content of approximately 20% by volume, topreferably between about 20 and 40% by volume and, where it has a watercontent of approximately 30% by volume, to preferably between about 10to 30% by volume.

In cases where primary extract solutions with benzene or alkyl benzenesor halogenated hydrocarbons as solvents are used, the solutions areextracted accordingly with alcohol or alcohol-water mixtures, preferablymethanol or ethanol and, with particular preference, methanol as theextractant, alcohol-water mixtures with a water content of preferablyfrom about 10 to 40% by volume and, with particular preference, fromabout 20 to 40% by volume, being used.

The ratio by volume of hydrocarbon phase to alcoholic aqueous phase inextraction stage A is variable within wide limits and, for reasons ofeconomy, is in the range of from about 1 to 10. Volume ratios of about 1to 4 are preferably applied. In cases where primary extract solutions inhalogenated hydrocarbons are used, the ratio by volume of halogenatedhydrocarbon phase to alcoholic-aqueous phase is generally in the rangeof from about 0.1 to 2 and preferably in the range of from about 0.2 to1.5.

To carry out extraction stage B, the hydrocarbon or halogenatedhydrocarbon phase resulting from extraction stage A can be delivered toextraction stage B with its solvent composition either intact ormodified within the scope of the mixtures used for extraction stage B.

In general, it has proved to be advantageous for extraction inextraction stage B of the process according to the invention, to use ahydrocarbon phase which consists of aliphatic and/or cycloaliphaticand/or aromatic hydrocarbons and which optionally has a cycloaliphaticand/or aromatic hydrocarbon content of less than about 50% by volume,preferably less than about 40% by volume.

Alcohol/water mixtures are generally used as extractant 2, the watercontent of the extractant preferably amounting to between about 10 and30% by volume.

It has proved to be particularly advantageous, for example forextraction stage B, to start with a hydrocarbon phase which containsabout to 30% by volume of cycloaliphatic and/or aromatic hydrocarbons,and to adjust the water content of extractant 2 to between about and 20%by volume and, with particular preference, to about 10% by volume. Forexample, it has proved to be advantageous to extract the hydrocarbonphase with an extractant 2 containing approximately 10% by volume ofwater when it has an aromatic hydrocarbon content of from about 10 to30% by volume, or with an extractant 2 containing approximately 20% byvolume of water when it has an aromatic hydrocarbon content of from O to10% by volume.

The ratio by volume of hydrocarbon phase to extractant 2 is variablewithin wide limits and, for reasons of economy, generally amounts tobetween about 0.1 and 1.0. Volume ratios of from about 0.1 to 0.6 arepreferred.

In the presence of a halogenated hydrocarbon phase for furtherextraction in extraction stage B, it has proved to be particularlyadvantageous to extract the halogenated hydrocarbon phase with aqueousmethanol containing from about 30 to 40% by volume of water, and tomaintain the ratio by volume of halogenated hydrocarbon phase toalcoholic-aqueous phase preferably within the range of from about 0.05to 0.2 and, with particular preference, within the range of from about0.05 to 0.1.

It has been found that, for separation by the process according to theinvention, the ratio by volume of hydrocarbon or halogenated hydrocarbonphase to alcoholic-aqueous phase in extraction stage B is best reducedto at least about half and preferably to at least one-third of thecorresponding ratio in extraction stage A.

The conditions applied in extraction stage B, especially the watercontent of the alcoholic-aqueous phase and the aromatic-fraction andcycloaliphatic-fraction content of the hydrocarbon phase, are bestadapted to the conditions preselected for extraction stage A so thatextraction stages A and B can be combined under the preferred conditionswith minimal outlay. Accordingly, the process according to the inventioncan be advantageously carried out by introducing an alcoholicaqueousprimary extract solution, optionally adjusted to a water content of fromabout 10 to 30% by volume by the addition of water, into extractionstage A, and using mixtures of an aliphatic hydrocarbon with from 10 to60% by volume of an aromatic hydrocarbon as extractant 1, extractionbeing carried out with a ratio by volume of hydrocarbon phase toalcoholic-aqueous phase of about 1 to 10. In the subsequent extractionstage B, the hydrocarbon phase resulting from extraction stage A isextracted with an extractant 2 comprising a lower aliphatic alcoholcontaining approximately 10 to 30% by volume of water. In extractionstage B, the ratio by volume of hydrocarbon phase of alcoholicaqueousphase is reduced to at least half and preferably to at least one-thirdof the corresponding ratio in extraction stage A, and a ratio by volumeof about 0.1 to l is maintained.

With the same solvent systems in extraction stages A and B, it is onlythe ratio by volume of hydrocarbon phase to alcoholic-aqueous phase thatcan be reduced in extraction stage B, and this is preferably reduced toabout one-fifth to one-tenth of the corresponding value in extractionstage A. In addition, it has proved to be particularly advantageous inextraction stage B a. either to reduce the water content of extractant 2by about 10 to 20% by volume in relation to the water content of thealcoholic-aqueous phase from extraction stage A with the same solventcomposition of the hydrocarbon phase in extraction stages A and B; or

b. where the primary extract solution and extractant 2 have the samewater content, to reduce the aromatic and/or cycloaliphatic hydrocarboncontent of the hydrocarbon phase to around 5 to 20% by volume by theaddition of an aliphatic hydrocarbon containing from 5 to 10 carbonatoms.

Measures (a) and (b) can, of course, also be combined.

Extraction stage C is best carried out by extracting thealcoholic-aqueous primary extract solution with an extractant whichconsists of the aforementioned aliphatic and/or cycloaliphatic and/oraromatic hydrocarbons.

It has proved to be advantageous, for example in extraction stage C, toadjust the water content of the primary extract solution to about 5 to30% by volume and preferably to about 10 to 20% by volume, and to use asextractant an aliphatic hydrocarbon or a mixture of an aliphatichydrocarbon with alicyclic or preferably aromatic hydrocarbons. Thecycloaliphatic or aromatic hydrocarbon content of extractant 3 can, forexample, amount to between about 0 and 50% by volume, preferably tobetween about 0 and 30% by volume.

In cases where primary extract solutions in benzene or alkyl benzenes orhalogenated hydrocarbons as solvents are used, an alcohol-water mixtureis, of course, used accordingly as extractant, methanol or ethanol watermixtures containing from about 10 to 40% by volume of water preferablybeing used, particularly preferred are methanol-water mixturescontaining from about 2040% by volume of water.

The ratio by volume of extractant 3 to the alcoholicaqueous phase isvariable within wide limits and, for reasons of economy, is generally inthe range of from about 0.l to 1. It is preferred to apply volume ratiosof about 0.2 to 0.6.

To carry out extraction stage D, the alcoholicaqueous phase emanatingfrom extraction stage C can be delivered to extraction stage D with itswater content either intact or modified within the scope of the mixturesused for extraction stage D.

For extraction stage D, it has proved to be advantageous to adjust thewater content of the alcoholicaqueous phase to between about 10 and 40%by volume and preferably to between about 10 and 30% by volume, and touse an extractant 4 containing aliphatic and/or cycloaliphatic and/oraromatic hydrocarbons. For example, where aliphatic hydrocarbons areused as extractant 4, it has proved to be advantageous to adjust thealcoholic-aqueous phase to be extracted to between about 10 and 20% byvolume. It is preferred to use mixtures of aliphatic with cycloaliphaticand/or aromatic hydrocarbons, and it is particularly preferred to usemixtures with aromatic hydrocarbons. The aromatic hydrocarbon content ofmixtures such as these can generally amount to between about and 90% byvolume and preferably amounts to between about 10 and 50% by volume.

The ratio by volume of extractant 4 to the alcoholic aqueous phase isvariable within wide limits and, for reasons of economy, it is generallymaintained in a range of from about 1 to 10. Volume ratios of about 1 to4 are preferably applied.

It has been found that, for separation by the process according to theinvention, it is best to increase the ratio by volume of the hydrocarbonphase to the alcoholic-aqueous phase in extraction stage D by at leastabout 5 times and preferably by at least about 20 times thecorresponding value in extraction stage C.

To carry out the process according to the invention, therefore, it isadvantageous to use in extraction stage C an alcoholic-aqueous primaryextract solution, optionally adjusted by the addition of water to awater content of from about to by volume, and to use an aliphatichydrocarbon, optionally in admixture with an aromatic hydrocarbon, asextractant 3, extraction being carried out with a ratio by volume ofhydrocarbon phase to alcoholic-aqueous phase of about 0.1 to I. In thesubsequent extraction stage D, the alcoholicaqueous phase resulting fromextraction stage C is extracted with an extractant 4 comprising amixture of aliphatic and aromatic hydrocarbons with an aromatichydrocarbon content of from about 10 to 50% by volume. The ratio byvolume of the hydrocarbon phase to the alcoholic-aqueous phase ispreferably increased to between at least about 5 times and at leastabout 20 times the corresponding value in extraction stage C, and avolume ratio of from about I to 10 is applied.

With the same solvent systems in extraction stages C and D, only theratio by volume of hydrocarbon phase to alcoholic-aqueous phase can beincreased in extraction stage D, preferably to between about 5 and 10times the corresponding value in extraction stage C.

Furthermore, it has proved to be particularly advantageous in extractionstage D a. either to increase the aromatic hydrocarbon content of thehydrocarbon phase used as extractant 4 by about 10 to 20% by volumewhere the water content of the alcoholic-aqueous phase in extractionstages C and D is the same, or

b. where the hydrocarbon phase of extraction stages C and D has the samesolvent composition, to increase the water content of thealcoholicaqueous phase by about 5 to 20% by volume in relation to thewater content of the aqueousalcoholic phase from extraction stage C.

Measures (a) and (b) can, of course, also be combined.

In the process according to the invention, the liquidliquid extractionsare carried out by conventional extraction methods. Thus, the individualextraction stages can be carried out, for example, by shaking inseparation funnels, by means of mixer-settler systems, and also bycountercurrent extraction in columns without stirrers such as, forexample, extraction spray towers or extraction towers with or without apacking, or by countercurrent extraction in columns with stirrers suchas, for example, Scheibel columns or RDC (rotating disc contactor)columns or by means of extraction centrifuges. Sieve-plate pulsationcolumns and RDC columns have proved to be particularly advantageous forcontinuous operation.

The extraction temperature for the individual extraction stages isvariable within wide limits. For practical reasons, extraction isgenerally carried out at temperatures of from 0 to 50C and preferably attemperatures of from 5 to 30C. For practical and economical reasons, theextractions are normally carried out under normal pressure, although, inprinciple, they could also be carried out under excess pressure, forexample in cases where particularly low-boiling extractants are used.

The neutral substances, bitter substances and tannins from thealcoholic-aqueous solutions or hydrocarbon solutions or halogenatedhydrocarbon solutions obtained by the process according to the inventioncan be separated from the solvent in the usual way, for example in arotary evaporator, falling-film evaporator or thin-layer evaporator.

One embodiment of the process according to the invention, in whichcountercurrent extraction columns are used for combining extractionstages A and B, is explained with reference to the flow chart in FIG. 1.The primary extract solution is introduced into extraction column Athrough pipe 1. Extraction stage A is carried out in column A, theextractant 1 being delivered in countercurrent to column A through pipe2 (hydrocarbon phase) while an alcoholic-aqueous solvent mixture, whichcorresponds to the solvent composition of the primary extract solution,is delivered to the head of column A through pipe 3. The tannins remainin the alcoholic-aqueous phase and are removed from the bottom of columnA through pipe 4. The bitter substances and neutral substances enter theextract and are removed at the head of column A through pipe 5 anddelivered to column B.

Extraction stage B is carried out in column B, the extractant 2 (amixture of alcohol and water) being delivered through pipe 7. Ahydrocarbon or hydrocarbon mixture, which corresponds to the solventcomposition of the hydrocarbon phase to be extracted, is deliveredthrough pipe 6.

The bitter substances are removed in alcoholicaqueous solution fromcolumn B through pipe 9. The neutral substances remain in thehydrocarbon phase and are removed from column B through pipe 8.

Another embodiment of the process according to the invention forcombining extraction stages C and D is explained with reference to theflow chart in FIG. 2:

The alcoholic-aqueous primary extract solution is introduced into theextraction column C through pipe 11. Extraction stage C is carried outin column C, the extractant 3 being delivered in countercurrent to thebottom of column C through pipe 12 (hydrocarbon phase), whilst a solventmixture, corresponding to the solvent composition of the primary extractsolution, is delivered to the head of column C through pipe 13.

The bitter substances and tannins remain in the alcoholic-aqueous phaseand are removed from column C through pipe 14. The neutral substancesenter the extract and are removed at the head of column C through pipe15 anddelivered to column D.

Extraction stage D is carried out in column D, the extractant 4(hydrocarbon mixture) being delivered through pipe 16. Analcoholic-water mixture, which corresponds to the solvent composition ofthe alcoholic-aqueous phase to be extracted, is delivered through pipe17.

The bitter substances are extracted in the hydrocarbon phase and areremoved from column D through pipe 18. The tannins are removed inalcoholic-aqueous solution from column D through pipe 19.

The extracts obtained by the process according to the invention can beused for the production of beer. The extracts can be used, for example,in the form of the alcoholic solutions obtained from the individualextraction stages or preferably following evaporation of the solvent.The extracts obtained by the process according to the invention areadvantageous in that the individual extracts which, in their entirety,contain all the ingredients essential for brewing, can be used in aprecisely defined quantity and in different phases of the brewingprocess involved in the production of beer. Accordingly, the ingredientscan be prevented from being adversely affected in terms of their effectduring the brewing process. For example, the hops can be aromatized withfull utilization of the bitter substances by separately adding theextracts of bitter and neutral substances.

Another advantage of the process according to the invention is that, incontrast to other separation processes such as, for example, steamdistillation or precipitation, the separation process according to theinvention is extremely gentle on the products themselves insofar as itis not carried out either at elevated temperature or in the presence ofsalts, acids or alkalis, so that the ingredients of the hops, some ofwhich are extremely sensitive, undergo no changes. Furthermore, nosubstances that are foreign to hops enter the extracts in the processaccording to the invention, with the result that the extracts can beused safely in physiological terms for the production of beer.

It must be regarded as extremely surprising that the hop ingredients,which represent a complex mixture of a variety of different types ofcompounds, can be separated by the process according to the invention,i.e. by a succession of extractions, into the three characteristicgroups of neutral substances, bitter substances and tannins.

The process according to the invention constitutes a considerabletechnical advance by allowing completely new techniques to be applied tothe production of beer. A large number of possible variations is createdby the periodically and quantitatively reproducible addition of thethree extracts during the brewing process.

EXAMPLE 1 35 kg of hops of the l-lallertauer Mittelfruher 1970 type,which were in the form of standard pressed hops and which, beforeprocessing, had been stored for a total of 3 months, were extracted with80 kg of methanol to prepare a primary extract solution. For thispurpose, the hops were size-reduced, introduced into four cylinderextraction columns in four 8.75 kg batches and percolated with thesolvent.

Percolation was carried out in such a way that the entire solvent wasintroduced into the first column and the solution trickling down wascollected successively in equal parts by volume. After the entirequantity of solvent had been added, more solvent was additionallyintroduced into the column in a quantity commensurate with that retainedby the hops as absorbed solution, so that the volume of the solutionflowing out of the bottom of the column was equal to the volume of thetotal solvent added at the head of the column. The 10 equal parts byvolume thus obtained, beginning with the first, were successivelyintroduced into the next column. After all 10 of the componentquantities from the first column had been added to the second column, additional solvent was again introduced into the second column in aquantity commensurate with that retained by the hops in the form ofabsorbed solution, with the result that the volume of the solutionflowing out of the bottom of the column was equal to the volume of thesolution added at the head of the column. The same procedure was adoptedfor the remaining columns.

1 12.2 liters of primary extract solution weighing 93.7 kg andcontaining 9.65 kg of hop extract, corresponding to 10.2% by weight, and4.05 kg of water, corresponding to 4.32% by weight, were obtained fromthe fourth column. 9.65 kg of hop extract corresponded to an extractionyield of 27.6% (based on the hops used). 5.64 (58.5%) of this extractwere soluble in n-hexane. This n-hexane-soluble fraction contained thebitter and neutral substances 4.01 kg (41.5%) were insoluble inn-hexane. This fraction insoluble in n-hexane contained the tannins.

EXAMPLE 2 50 kg of the hops of the Tettnanger 1971 type, which were inthe form of non-pressed baled hops and which had been stored for a totalof 5 months before processing, were extracted with 61.28 kg of methanolto prepare a primary extract solution. For this purpose, the hops weresize-reduced, introduced into six cylindrical extraction columns in six8.33 kg batches and percolated with the solvent as in Example 1.

92.68 liters of primary extract solution weighing 78.75 kg andcontaining 12.05 kg of hop extracts, corresponding to 15.3% by weight,and 3.75 kg of water, corresponding to 4.76% by weight, were obtainedfrom the sixth column. The 12.05 kg of hop extract corresponded to anextraction yield of 24.1% and contained 6.09 kg (50.5%) of neutral andbitter substances and 5.96 kg (49.5%) of tannins.

EXAMPLE 3 65 kg of the hops of the Hallertauer Nordbrauer 1970 typewhich were in the form of standard pressed hops and which had beenstored for a total of 11 months before processing, where extracted with63.0 kg of methanol to prepare a primary extract solution. For thispurpose, the hope were size-reduced, introduced into eight cylindricalextraction columns in eight 8.13 kg batches and percolated with thesolvent as in Example 1.

98.02 liters of primary extract solution weighing 85.8 kg and containing16.0 kg of hop extract, corresponding to 18.75% by weight, and 7.22 kgof water, corresponding to 8.42% by weight, were obtained from theeighth column. The 16.08 kg of hop extract corresponded to an extractionyield of 24.75% and contained 9.25 kg (57.5%) of neutral and bittersubstances and 6.834 kg (42.5%) of tannins.

EXAMPLE 4 .5 kg of hops of the Spolter 1968 type, which were in the formof standard pressed hops and which had been stored for a total of 18months before processing, were extracted with 69.5 kg of methanol toprepare a primary extract solution. For this purpose, the hops weresize-reduced, introduced into six cylindrical extraction columns in six7.5 kg batches and percolated with the solvent as in Example 1.

99.95 liters of primary extract solution weighing 84.92 kg andcontaining 10.62 kg of hop extract, corresponding to 12.51% by weight,and 4.80 kg of water, corresponding to 6.46% by weight, were obtainedfrom the sixth column. The 10.62 kg of hop extract corresponded to anextraction yield of 23.6% and contained 3.95 kg (37.2%) of neutral andbitter substances and 6.67 kg (62.8%) of tannins.

EXAMPLE 5 50 kg of hops of the Hallertauer Mittelfruher 1970 type, whichwere in the form of standard pressed hops and which had been stored fora total of 8 months before processing, where extracted with 68.0 kg ofmethanol to prepare a primary extract solution. For this purpose, thehops were size-reduced, introduced into six cylindrical extractioncolumns in six 8.33 kg batches and percolated with the solvent as inExample 1.

99.80 liters of primary extract solution weighing 84.84 kg andcontaining 12.05 kg of hop extract, corresponding to 14.18% by weight,and 4.89 kg of water, corresponding to 5.76% by weight, were obtainedfrom the sixth column. The 12.05 kg of hop extract corresponded to anextraction yield of 24.2% and contained 6.14 kg (51.0%) of neutral andbitter substances and 5.91 kg (49.0%) of tannins.

EXAMPLE 6 50 kg of hops of the Tettnanger 1968 type, which were in theform of non-pressed baled hops and which had been stored for a total of2 months before processing, were extracted with 75.0 kg of ethanol toprepare a primary extract solution. For this purpose, the hops weresize-reduced, introduced into six cylindrical extraction columns in six8.33 kg batches and percolated with the solvent as in Example 1.

1 10.3 liters of primary extract solution weighing 92.28 kg andcontaining 1 1.25 kg of hop extract, which corresponds to 5.45% byweight, were obtained from the sixth column. The 11.25 kg of hop extractcorresponded to an extraction yield of 22.5% and contained 6.83 kg(60.7%) of neutral and bitter substances and 4.42 kg (39,3%) of tannins.

EXAMPLE 7 50 kg of hops of the Nordbrauer 1970 type, which were in theform of standard pressed hops and which had been stored for a total of1.5 months before processing, were extracted with 82.5 kg of n-propanolto prepare a primary extract solution. For this purpose, the hops weresize-reduced, introduced into seven cylindrical extraction columns inseven 7.15 kg batches and percolated with the solvent as in Example 1.

1 17.1 liters of primary extract solution weighing 98.63 kg andcontaining 10.90 kg of hop extract, corresponding to 11.05% by weight,and 5.73 kg of water, corresponding to 5.81% by weight, were obtainedfrom the seventh column. The 10.90 kg of hop extract corresponded to anextraction yield of 21.8% and contained 7.44 kg (68.2%) of neutral andbitter substances and 3.46 kg (31.8%) of tannins.

EXAMPLE 8 50 kg of hops of the Hallertauer Mittelfruher 1971 type, whichwere in the form of standard pressed hops and which had been stored fora total of 4 months be fore processing, were extracted with 71.5 kg ofipropanol to prepare a primary extract solution. For this purpose, thehops were size-reduced, introduced into seven cylindrical columns inseven 7.15 kg batches and percolated with the solvent as in Example 1.

104.74 liters of primary extract solution weighing 87.02 kg andcontaining 9.92 kg of hop extract, corresponding to l 1.4% by weight,and 5.6 kg of water, corresponding to 6.94% by weight, were obtainedfrom the seventh column. The 9.92 kg of hop extract corresponded to anextraction yield of 19.83% and contained 6.289 kg (63.4%) of neutral andbitter substances and 3.630 kg (36.6%) of tannins.

EXAMPLE 8a 20 kg of hops of the Hallertauer Mittelfruher 1972 type,which were in the form of conventional pressed hops and which had beenstored for a total of 6 months before processing, were extracted with33.755 kg of methanol to prepare a primary extract solution. For thispurpose the hops were sizereduced, introduced into six cylindricalextraction columns in six 3.333 kg batches and percolated with thesolvent as in Example 1.

48.408 liters of primary extract solution weighing 40.905 kg andcontaining 5.064 kg of hop extract, corresponding to 12.38% by weight,and 2.086 kg of water, corresponding to 5.10% by weight, were obtainedfrom the sixth column. The 5.064 kg of hop extract corresponded to anextraction yield of 25.32% and contained 2.719 kg (53.7%) of neutral andbitter substances and 2.345 kg (46.3%) of tannins.

EXAMPLE 8b .20 kg of hops of the Hallertauer Nordbrauer 1972 type, whichwere present in the form of standard pressed hops and which had beenstored for a total of 6 months before processing, were extracted with35.827 kg of methanol to prepare a primary extract solution. For thispurpose, the hops were sized-reduced, introduced into six cylindricalextraction columns in six 3.333 kg batches and percolated with thesolvent as in Example 1.

51.410 liters of primary extract solution weighing 43.441 kg andcontaining 5.226 kg of hop extract, corresponding to 12.03% by weight,and 2.388 kg of water, corresponding to 5.50% by weight, were obtainedfrom the sixth column. The 5.226 kg of hop extract corresponded to anextraction yield of 26.13% and contained 3.465 kg (66.3%) of neutral andbitter substances and 1.761 kg (33.7%) of tannins.

EXAMPLE 8c 23 kg of hops of the Hallertauer Mittelfruher 1971 type,which were present in the form of standard pressed hops and which hadbeen stored for a total of 3 months before processing, were extractedwith 36.293 kg of ethanol to prepare a primary extract solu- 15 tion.For this purpose, the hops were sizereduced, introduced into eightcylindrical extraction columns in eight 2.875 kg batches and percolatedwith the solvent as in Example 1.

EXAMPLE 8d 35 kg of hops of the I-lallertauer Mittelfruher 1972 type,which were present in the form of standard pressed hops and which hadbeen stored for a total of 6 months before processing, were extractedwith 71.776 kg of methylene chloride to prepare a primary extractsolution. For this purpose, the hops were sizereduced, introduced intoseven cylindrical extraction columns in seven kg batches and percolatedwith the solvent as in Example 1.

58.553 liters of primary extract solution weighing 76.997 kg andcontaining 5.128 kg of hop extract, corresponding to 6.66% by weight,and 0.093 kg of water, corresponding to 0.12% by weight were obtainedfrom the seventh column. The 5.128 kg of hop extract corresponded to anextraction yield of 14.65% and contained 4.972 kg (96.96%) of neutraland bitter substances and 0.156 kg (3.04%) of tannins.

EXAMPLE 8e 40 kg of hops of the Hallertauer Nordbrauer 1972 type, whichwere in the form of standard pressed hops and which had been stored fora total of 6 months before processing, were extracted with 51.737 kg ofbenzene to prepare a primary extract solution. For this purpose, thehops were size-reduced, introduced into five cylindrical extractioncolumns in five 8 kg batches and percolated with the solvent as inExample 1.

63.832 liters of primary extract solution weighing 57.449 kg andcontaining 5.676 kg of hop extract, corresponding to 9.88% by weight,and 0.036 kg of water, corresponding to 0.06% by weight, were obtainedfrom the fifth column. The 5.676 kg of hop extract corresponded to anextraction yield of 14.19% and con tained 5.103 kg (89.90%) of neutraland bitter substances and 0.573 kg (10.10%) of tannins.

EXAMPLES 9 to 110 Separation of the hop constituents in the separationstages A, B, C and D is described in tabular form in the followingExamples 9 to 110.

The details of the individual Examples relate to a succession ofextractions in a separation funnel. The results of these Examples canalso be applied to any other batch-type distributing apparatus or canform the basis for the design of continuous-type extraction columns.

The extractions on which the individual Examples are based were carriedout in accordance with the flow chart illustrated in FIG. 3.

In FIG. 3, S represents the extractant (solvent), H the solution to beextracted, and R a solvent mixture which corresponds in solventcomposition to the solution to be extracted.

According to the flow chart, the phase H to be extracted is extractedwith the extractant S in the extrac- 16 tion stage E1. The resultingphases S (solvent phase obtained during extraction) and R (raffinatephase obtained during extraction) were each subjected to anotherextraction in the extraction stage E2.

In extraction stage E2, the phase R was extracted with fresh extractantS and the phase S with fresh solvent R which corresponded to thesolution to be extracted. The solvent phases S and S formed and theraffinate phases R and R were subjected to further extractions in theextraction stage E3, as indicated by the arrows. R was extracted withsolvent S, S with fresh R and R with S The resulting phases S S and Sand R R and R could be delivered to a different extraction stage E4, inaccordance with the flow chart, and similarly to the further extractionstages E5, E6, etc.

Tables 1 to 8 contain the following particulars with reference toExamples 9 to 110:

The column headed Primary Extract Solution Used (Tables 1, 2, 2a, 5, 6,6a) sets forth the origin of the extract solution by reference to thepreceding Examples in which the same solution was obtained i.e., thesolutions used have the same ingredients as the solvent system used inthe particular preceding Example identified in the column. (With respectto the column headed Solution Used cf. footnote 3 and 4).

In cases where primary extract solutions of Example 1 to 8 are used(i.e., in Tables 1, 2, 2a,5, 6 and 6a), the primary extract solutionreferred to is adjusted to the water content specified in the columnheaded Alcoholic Phase and used in the quantity specified in the lattercolumn. For instance, the primary extract solution used in Example 9(relating to separation stage C) was the same as prepared in Example 1(utilizing methanol as the solvent) and the solvent used in Example 9was adjusted to one liter with the water content of 10% (i.e. of(aqueous) methanol, as stated in Example 9).

In those cases where Examples 9 to l 10 are referred to in the SolutionUsed column (i.e., in Tables 3, 4, 4a, 7, 8 and 8a), the ingredients ofthe raffinate or solvent phase are freed from the solvent if necessaryby concentration through evaporation (for example at 40C/l0 to mm Hg ina rotary evaporator), and are subsequently dissolved in the quantity ofsolvent specified (also see footnotes 3 and 4 below). For instance, inExample 31 (relating to Separation Stage D), the Solution Used was asolution of the ingredients of the raffinate phase of Example 9dissolved in 0.7 liters of 90% (by vol.) aqueous methanol, i.e., thesolvent stated in the column Alcoholic Phase in Example 31.

The column headed Solvent System shows the solvents and quantities ofsolvent used for extraction. The quantities of solvent specified in thecolumn headed Quantity in 1. relate in each case to one extraction stage(El, E2, etc.).

The results are expressed in terms of the content, in the recoveredsolvent and raffinate phases, of neutral substances N, bitter substancesB and tannins G, the solvent phases S and raffinate phases R which wereselected for determining the content of ingredients and on which thevalues are based, being derived from the drawings showing 2, x and y.(The remaining fractions were discarded).

The footnotes which apply for the following Tables are located after thelast Table in this series, viz., Table 8a, below.

Table 1 Separation Stage C Solvent phase Raf'finate phase recoveredrecovered Alcoholic-aqueous Primary Solvent System No. of HC*-solutinsolution Extract Hydrocarbon phase Alcoholic phase extraccontent ofcontent of Ex. Solution Composition Quan- Composition Quantion NS NS No.Used (parts by tity (mixture tity stages BS BS (Ex.No.) volume) in l.with water) in I. z x T y T N= 5.23g =96.2% N= 004g 0.0% 9 1 pentane0.44 90% by vol. 1 9 -9 B= 0.21g 3.8% 1-5 B= 33.43g =50.0% fractionmethanol T= 0 g O T= 33.33g =49.9%

N=34.2lg =94.6% N= 0.3 lg 0.1% 2 hexane 3.50 90% by vol. 5 11 6-1 1 B=1.93g 5.3% 16 B=2l 1.88g =43.0% fraction methanol T= 0.02g 0.1%T=280.27g =56.9%

N=34.75g 95.8% N= 0.49g 0. l 11 6 hexane 2.75 90% by vol. 5 l1 6ll B=1.51g 4.2% l-6 B=203.99g =52.1% fraction ethanol T= 0g 0% T=l 87.36g=47.9%

N= 5.95g =95.4% N= 0.04,; 0.l% 12 e heptane 1.16 89.5% by 1 26 14-26B=0.29g 4.6% l-13 B-- 34. =4s.0 7(

fraction vol. ethanol T= 0.0lg 0. 1% T= 36.91g =52.0%

N= 471g =95.6% N= 003g 0.1% 13 1 octane 0.46 80% by vol. 1 l 1 6-11 B=0.21g 4.4% 1-6 B= 29.84g =49,57( fraction methanol T= 0g 0% T= 30.41 g=50,4%

N= 6.64g =97.4% N= 0.02g 0.l% l4 6 octane 0.91 90% by vol. 1 14 8-14 B=0.18g 2.6% 1-7 B= 37.59g =5l.2% fraction ethanol T= 0g 0% T= 35.85g=48.8%

N= 6.22g =99.1% N= 0.02g 0.l% l5 2 decane 0.60 90% by vol. 1 26 14-26 B=0.05g 0.9% l-l 3 B= 43.78g #ZJZ fraction methanol T= 0g 0% T= 58.82g=57.3%

N= 6.23g =97.9% 001g 0. 1% 16 6 decane 1.16 90% by vol. 1 26 14-26 B=0.13g 2.1% l-l2 B= 35.57g =50.07z fraction ethanol T= 0g 0% T= 35.50g=30.0%

N= 5.76g =97.2% N= 0.02g 0.l% 17 7 decane 1.35 80% by vol. 1 16 9l6 B=0.17g 2.8% 1-8 B= 34.38g =59.8% fraction npropanol T= 0g 0% T= 23.10g=40.2%

N= 5.15g =70.2% N= 0.40g 0.4% 18 2 cyclohexane 1.04 85% by vol. 1 31l5-3l B= 2.18g =29.8% ll7 B= 31.70g =36.0%

methanol T= 0g 0% T= 56.9g =63.6%

Table 2 Separation Stage C Separation of the neutral substances from thebitter substances and tannins Solvent phase Raffinate phase recoveredrecovered Alcoholic-aqueous Primary Solvent System No. of HC*s0lutionsolution Extract Hydrocarbon phase Alcoholic phase extraccontent ofcontent of Ex. Solution Composition Quan- Composition Quantion NS NS NoUsed (parts by tity (mixture tity stages BS BS (Ex.No.) volume) in l.with water) in l. 2 x T y T N= 7.40g =99.5% N= 0.01g 0.l% 19 lcyclohexane 0.34 70% by vol. 2 26 -26 B= 004g 0.5% B= 46.93g =47.0%

l-l2 methanol T= 0 g 0 T= 52.98g =53.0%

hexane N= 9.47g =96.9% N= 0.05g 0.l% 20 1 fraction 1.44 90% by vol. 2 169-16 B= 030g 3.1% l-8 B= 59.95g =47.5% benzene methanol T= 0 g 0 T=66.28g =52.5% (10:1)

hexane N= 5.56g =99.6% N== 0.01g 0.l% 21 2 fraction 0.28 by vol. l 2615-26 B= 0.02g 0.4% 1-12 B= 34.00g =38.7% benzene methanol T= 0 g 0 T=53.77g =61.3% 10:1

hexane N= 8.6lg =97.4% N= 004g 0.l% 22 3 fraction 0.22 80% by vol. 1 2614-26 B= 0.23g 2.6% l-l 3 B= 49.64g #SAZ benzene methanol T 0 g 0 T=59.62g =54.6% (7:3)

hexane N= 5.37g #537; N= 0.04g 01% 23 6 fraction 0.5 80% by vol. 1 2614-26. B= 0.26g 4.7% l-l 3 B= 30.7 g #787: benzene ethanol B=0 g 0 T=33.54g =52.1%

Table 2 -Continued Separation Stage C I Separation of the neutralsubstances from the bitter substances and tannins recovered recoveredAlcoholic-aqueous Primary Solvent System No. of HC.*solution solutionExtract Hydrocarbon phase Alcoholic phase extraccontent of content ofEx. Solution Composition Quan- Composition Quan-' tion NS NS No. Used(parts by tity (mixture tity stages B5 B5 (Ex.No.) volume) in l. withwater) in l. 2 x T y T hexane N= 5.62g 33.8% 005g 0.1% 24 5 fraction0.24 90% by vol. 1 1 1 6-1 1 B 0.37g 6.2% 1-6 B= 40.74g $2.471 toluenemethanol T=0 g 0 7c T= 57.5 g =57.5% (6:4

hexane N= ).57g =96.1% N= 0.07g 0.1% 25 3 fraction 0.26 80% by vol. 1 137-13 B= 0.39g 3.9% 1-7 B= 54.67g =47.771 cyclohexane methanol T= 0 g 071 T 59.87g =52.2% (7:3)

hexane N= 5.62g =99.671 N= 0.01 g 0.1% 26 6 fraction 0.55 80% by vol. 126 15-26 B= 0.02g 0.4% 1-12 B= 32.29g =48.9% cyclohexane ethanol T= 0 g0 7! T= 33.71g =51.l% (:1

heptane N=26.43g ==97.67 N= 0.12g 0.l% 27 2 fraction 3.44 93.2% by 4 169-16 B= 0.66g 2.4% 1-8 B=164.01g =40.5% begzene vol. methanol T= 0 g 0T=241.12g =S9.5% l :l

heptane I N=11.83g =s5.s% N= 0.30 0.2% 28 6 fraction 1.82 90% by vol. 226 13-26 B= 1.96g =14.2% 1-14 B= 67.89g =47.9% benzene ethanol T= 0 g 0T= 73.67g =51.9% 10:3)

octane N= 5.95g =96.0% N= 0.04g 0.1% 29 1 fraction 0.5 80% by vol. 18-15 B= 0.25g 4.0% 1-8 B= 34.20g =51.9% xylene ethanol T= 0 g 0 T=31.60g =48.0% (6:4)

decane N= 9.51g =36.9% N= 0.05g 0.1% 30 3 fraction 0.51 90% by vol. 1 2614-20 B= 0.30g 3.1% l-13 B= 54.69g =45.2% benzene methanol T= 0 g 0 T=66.36g =54.7%

Table 2a Separation Stage C Separation of the neutral substances fromthe bitter substances and tannins Solvent phase Raffinate phaserecovered recovered Alcoholic-aqueous Primary Solvent System No. ofHC*-so1ution solution Extract Hydrocarbon phase Alcoholic phaseextraccontent of content of Ex. Solution Composition Quan- CompositionQuantion NS NS No. Used (parts by tity (mixture tit stages BS BS(Ex.No.) volume) in 1. with water) in z x T y T N= 4.67g =99.7% N= 0.00g0.0% 30a 3 cyclooctane 0.425 90% by vol. 0.500 20-35 B= 0.01g 0.03% 1-16B=26.92g 45.0

methanol T= 0.00g 0.0% T=32.88g =55.0%

octane N= 2.94g =98. 1% N= 0.01g 0.1% 30b 2 fraction 0.170 80% by vol.0.500 16 9-16 B= 0.06g 1.9% 1-8 B=18.25g =40.3% cycglohexane methanol T=0.00g 0.0% T=27.07g =59.7%

hexane N= 5.20g =98.8% N= 0.01g 0.1% 30c 8b xylene 0.196 90% by vol.1.000 8 5-8 B= 0.06g 1.2% l-4 B=49.46g =60.7%

(6:4) methanol T= 0.00g 0.0% T=32.09g =39.37%

N== 3.43g =99.9% N= 0.00g 0.0% 30d 1 benzene 0.045 70% by vol. 0.50028-50 B= 0.01g 0.1% 1-23 B=21.34g =37.6% methanol T= 0.00g 0.0% T=35.48g=62.4%

N= 3.433 =99.7% N= 0.003 0.0% 30c 8b benzene 0.068 70% by vol. 0.750 5028-50 B== 0.0lg 0.8% 1-23 B==21.34g =67.6% methanol T= 0.00g 0.0%T=35.48g =62.4%

- N= 4.263 -97.8% N= 0.02g 0.1% 30] 2 benzene 0.070 40% by vol. 1.00032-60 B- 0.10; 2.2% 1-29 3-26.45g =35.8% methanol T- 0.003 I 0.0%T-47.34g =64.1%

. N= 4.24; -%.m N- 0.03; 0.m 30g 6 benzene 0.090 70% by vol. 1.000 34-65B- 0.17g 3.9% l-32 B-24.33g 453; ethanol T- 0.00; 0.0% T-29.39g 54.7%

N- 5.59; -99.9% N- 0013-0196 30f 8e benzene 0.043 by vol. 0.500 50 28-50B- 0013 0.1% 1-23 13-21335 82.9% methanol T 0.003 I 0.0% T 4.413 =17.1%

Solvent phase Raffinate phase Table 4a Continued Separation Stage DSeparation of the bitter substances and the tannins Solvent phaseRaffinate phase recovered recovered Alcoholic-aqueous Solvent System No.of HC*solution solution Hydrocarbon phase Alcoholic phase extraccontentof content of Ex. Solution Composition Quan- Composition Quantion NS NSNo. Used (pans by tity (mixture tity stages BS BS (Ex.No.) volume) in l.with water) in 1. z x T y T N= 0.00g N= 0.00g 0.0% 30d b 1.054 90% bvol. 0500 6-10 B= 8.71g =99.7% l5 B= 0.02g 0.2% al... T= 0.02g 0.3%T=l0.72g =99.s%

N= 0.01 g N= 0.00g 0.0% 0v 1% 57e s benzene 2.298 by vol. 5.850 5 3-5 B=9.00g =l00.0% l-3 B= 0.02g 1.0%

methanol T= 0.01g T 1.86g =99.0%

j N= 0.02g 0.1% N= 0.00g 0.0% 57f 30 benzene 0.784 60% by vol. 2.000 53-5 B=24.54g 99.5% l-3 B= 0.05g 0.1%

methanol T= 0.09g 0.4% T=43.92g =99.9%

N= 003g 0.1% N= 0.00g 0.0% 57g 30g benzene 1.790 by vol. 2.000 9 5-9B=20.6lg =99.4% l-S B= 0.08g 0.3%

ethanol T= 0.10g 0.5% T=24.89g =99.7%

N= 000g 00% N= 0.00g 0.0% 57h 30/1 benzene 7.840 60% by vol. 20.507 53-5 B=3l.99g 99.8% l-3 B= 0.07g 0.2%

methanol T= 0.06g 0.2% T=26.82g =99.8%

Table 5 Separation Stage A Separation of the neutral and bittersubstances soft resins) from the tannins- Solvent phase Raffinate phaserecovered recovered Alcoholic-aqueous Primary Solvent System No. ofHC*-solution solution Extract Hydrocarbon phase Alcoholic phaseextraccontent of content of Ex. Solution Composition Quan- CompositionQuantion No. Used (pans by tity (mixture tity stages SRqoft resinsSR=soften resins (Ex.No.) volume) in l. with water) in 1. z X T=tanninsy T=tannins 58 7 heptane 2.44 70% by vol. 1 7 4-7 39R?;2.59g SR= 0.18g0.9%

. 6 fraction n-propanol T= 0.10g l- T=19.74g =99.1%

59 7 octane 5.0 by vol. 0.5 9 5-9 gl9l=8i274.85g SR= 0.09g 0.7%

t 0 fraction n-propanol T= 0.05g 1-5 T=l 1.37g =99.3%

60 8 octane 3.0 80% by vol. 0.5 l 1 6-11 SR=21.66g SR= 0.] lg 1.0%

97.5% fraction i-propanol T= 0.55g l-6 10.33g =99.0%

61 8 nonane 3.6 80% by vol. 3.6 6 46 SR=73.55 g SR= 0.09g 0.2%

99.9% fraction methanol T= 0.88g 1-3 T=53.54g =99.8%

62 2 cyclopentane 2.30 80% by vol. 1 5 3-5 .05g SR= 0.18g 0.4%

.7 methanol T= 0.16g l-3 T=50.01 g =99.6%

63 l cyclooctane 1.67 70% by vol. 1 5 7 3-5 gl9l=374.l6g SR= 0.08g 0.3%

.9 a methanol T= 0.04g l-3 T=24.95g )9.7%

hexane SR=37.l lg SR= 0.24g 0.9%

99.4% 64 3 fraction 4.05 by vol. 0.5 13 7-13 T=01g 1-7 T=26.39g =99.1%

6 10:1 methanol hexane SR=29. 10g SR= 0.04g 0.1%

99.8% 65 4 fraction 3.5 80% by vol. 1 8 58 T= 0.977g l-4 T--48.3lg=99.9%

0.2 a benzene( 8:2) methanol hexane SR=27.97g SR= 0.093 0.2%

Table -Continued Separation Stage A Separation of the neutral and bittersubstances soft resins) from the tannins Solvent phase recoveredAlcoholic-aqueous Primary Solvent System No. of HC*-so1ution I solutionExtract Hydrocarbon phase Alcoholic phase extraccontent of content ofEx. Solution Composition Quan- Composition Quantion No. Used (parts bytity (mixture tity stages SR=soft resins SRqoften resins (Ex.No.)volume) in 1. with water) in l. 7. x T=tannins y T=tannins 66 4 fraction2.5 75% by vol. 1 7 4-7 T= 0.19g 1-4 T=46.66g =99.8%

0.7% benzene(6:4) methanol hexane SR=26.98g Sr= 0.07g 0.1%

99.4% 67 4 fraction 2.8 70% by vol. 1 5 35 T= 0.16;; 1-3 T=45.59g=99.97r

0.6% benzene(6:4) methanol hexane SR=47.08g SR= 0.16g 0.5%

99.8% 68 6 fraction 6.0 90% by vol. 1 12 7-12 T= 0.12g =0.2% 1-6T=29.50g =99.5%

benzene ethanol :1

hexane SR=44.12g =100. SR= 0.02g 0.1%

69 6 fraction 4.3 90% by vol. I 26 -26 T= 0.02g 1-12 T=26.83g =99.9%

0.1% benzene(7z3) I hexane SR =45.73g SR= 0.35g 1.2%

99.4% 70 6 fraction 3.3 80% by vol. 1 8 5-8 T= 0.27g 0.6% 1-3 T=28.96g=98.8%

benzene( 5 :5) ethanol Table 6 Separation Stage A Separation of theneutral and bitter substances soft resins) from the tannins Solventphase Raffinate phase recovered recovered Alcoholic-aqueous PrimarySolvent System No. of HC*so1ution solution Extract Hydrocarbon phaseAlcoholic phase extrac content of content of Ex. Solution CompositionQuan- Composition Quantion No. Used (parts by tit (mixture tity stagesSR=soft resins SR=soft resins (Ex.No.) volume) in with water) in 1. z xT=tann|ns y T=tannins hexane 71 6 fraction 4.1 80% by vol. 6 4-6g9=49g80g SR= 0.05g 0.1% toluene(6:4) ethanol T= 0.03g 0.1% 1-3 T=29.59g=99.9%

hexane SR'50.23g SR= 0.04g 0.1%

=99.9% 72 2 fraction 3.2 80% by vol. 6 4-6 T= 0.05g 0.1% 1-3 T=48.14g99.9%

xylene(6:4) methanol hexane SR=70.43g SR= 033g 0.6%

. 39970 73 4 fraction 3.0 80% by vol. 9 5-9 T= 0.31g 0.4% 1-5 T=50.55g=99.4%

xylene( 5:5) methanol hexane SR=46.51g SR= 0.06g 0.2%

=99.9% 74 6 fraction 4.8 80% by vol. 6 46 T= 0.04g =0.1% 1-3 T=29.81g=99.8%

xylene( 5:5) ethanol heptane SR=30.92g SR= 0.10g 0.2%

=99.5% 75 4 fraction 2.73 by vol. 5 3 5 T= 0.17g =0.5% 1-3 T=5l.94g=99.8%

benzene( 8:2) methanol heptane SR=43.43g SR= 0.08g 0.2%

=99.8% 76 5 fraction 2.13 70% by vol. 5 3-5 T: 0.1 1g 0.2% 1-3 T=41.33g=99.8%

benzene methanol 10:1)

heptane SR=33.83g SR=0.09g 0.4%

=99.8% 77 1 fraction 1.79 70% by vol. 5 3-5 T= 0.08g 0.2% 1-3 T=24.42g=99.6%

benzene( 8 :2) methanol heptane SR=47.52g SR= 0.19g 0.6%

Table 6 Continued Separation Stage A Separation of the neutral andbitter substances (=soft resins) from the tannins recovered recoveredAlcoholic-aqueous Primary Solvent System No. of HC*solution solutionExtract Hydrocarbon phase Alcoholic phase extraccontent of content ofEx. Solution Composition Quan- Composition Quantion No. Used (parts bytity (mixture tity stages SR=soft resins SR=soft resins (Ex.No.) volume)in l. with water) in 1. z x T=tannins y T=tannins 78 6 fraction 7.51 85%by vol. 1 9 5-9 T= 0.17g 0.4% [-5 T=29.87g =99.4%

benzene ethanol :1

heptane SR=37.24g SR= 0.09g 0.4%

=99.8% 79 6 fraction 2.01 by vol. 1 5 3-5 T= 006g 0.2% 1-3 T=23.92 g=99.6%

benzene ethanol 10:1

octane SR=33.95g SR= 0.09g 0.4%

99.8% 80 1 fraction 1.40 by vol. 1 5 3-5 T= 0.07 g 0.2% 1-3 T=24.57g=99.6%

benzene( 7:3) methanol octane SR=46.54g SR=0.16g 0.4%

=99.6% 81 5 fraction 4.5 80% by vol. 1 7 4-7 T= 0.17g =0.4% 1-4 T=44.06g99.6%

cyclohexane methanol (5:2)

82 4 cyclopcntane 5.69 90% by vol. 1 9 5-9 il fi36g SR= 0.10g 0.2%

. L benzene(7:3) methanol T= 0.20g 0.6% l5 T='53.37g =99.8%

83 5 cyclohexane 1.36 70% by vol. 1 5 3-5 SRfllBZg SR= 007g 0.2%

=99.9% benzene methanol T= 0.05g 0.1% [-3 T=42.16g =99.8% 10:1

Table 6a Separation Stage A Separation of the neutral and bittersubstances soft resins) from the tannins Solvent phase Raffinate phaserecovered recovered Alcoholic-aqueous Primary Solvent System No. ofHC*-solution solution Extract Hydrocarbon phase Alcoholic phaseextraccontent of content of Ex. Solution Composition Quan- CompositionQuantion No. Used (parts by tity (mixture tity stages SR=soft resinsSR=.ioft resins (Ex.No.) volume) in l. with water) in 1. z x Tqannins yT=tannins octane 5.05g N= 0.0lg 0.l%

=l5.5% 83a 8 fraction 1.613 by vol. 0.750 6 4-6 B= 27.50g =84.4% l-3 B=0.03g 0.2% benzene(7:3) isopropanol T= 0.02g =0.1% T= 18.60g 99.8%

octane N= 3.1 1g N= 0.01g 0.1%

=13.7% 83b 5 fraction 3.450 by vol. 0.500 8 5-8 k 19.58g =86.2% 1-4 B=0.03g 0.2%

cyclohexane ethanol T= 0.04g 0.2% T= 21.41g 99.8% (723) N=28.21g =1 5.5%N= 0.0lg 0. 1% 83c 3 benzene 2.225 80% by vol. 2.500 6 4-6 B=155.85g l-3B= 0.18g 0.1%

=84.4% methanol T= 0.15g T=l35.21g 99.9%

N= 5.25g N= 0.01g 0.0% =l4.5% 83d 2 benzene 0.82 60% by vol. 1.000 5 3-5B= 30.75g =85.l% 1-3 B= 0.13g 0.4%

ethanol T== 0.15g 0.4% T= 134.99g 99.6%

N= 3.66g N= 0.00g 0.0% =15.6 83e 6 benzene 1.045 80% by vol. 0.500 6 4-6B= 19.86g 2476 l-3 B= 0.02g 0.1%

ethanol T= 0.02g T= 15.09g 99.9%

N=15.36g =2l.5% N= 0.01g 0.1% 83f 8 benzene 0.894 80% by vol. 1.000 64-6 B= 56.2lg =78.5% l-3 B= 0.06g 0.8% methanol T= 0.01g T= 7.97g 99.2%

N= 7.99g N= 0.01g 0.1%

Solvent phase Raftinate phase Table 6a Continued Separation Stage ASeparation of the neutral and bitter substances so ft resins) fromthetannins Raffinate phase recovered Solvent phase Alcoholic-aqueoussolution No. of

Solvent System HC*solution extrac-J content of content of Hydrocarbonphase Alcoholic phase Quant1on tity stages in 1. z

Quan- Composition tity (mixture I in l. with water) Primary Extract ExSolution. Composition No. Used (parts by Ex.No.) volume) Taanninsff0.405 60% by vol.

ethanol benzene B= 0.01g 0.1% T= 12.02g 99.9%

0.235 70% by vol.

methanol toluene 2-4 B= 20.86g =s4.0% 1-3 B= 0.26; 1.6%

T= 0.20g 0.8% T= 15.85g 98.3%

1.180 80% by vol.

ethanol xylene 0.200 70% by vol.

methanol methylene chloride 1.000 70% by vol.

methanol 8d methylene chloride %& W 9 9 gg 6 .2 0.1 BT- 2 l %6 W 0 4: s8 e 8 c m m 20 3 .m w BT w a a 3 e m B m em 4 09:! m 7 S c n k .mm ..0M. 0 H mm M P1 1 m 1 I U 6 n e f ym 0 b3 W u Om m 6 a D- W 0 0 e we yMmm h n mC w... m 0 .m d s M a n c 8 1 m M 3 r 8 w Raffinate phaserecovered Solvent phase r'ecovered Alcoholic-aqueous solution content ofHC* solution content of No. of

extrac- Solvent System Hydrocarbon phase Alcoholic phase NS BS T NS BS TQuannon tity stages 1 n l z= Quan- Composition tity (mixture in 1. withwater) 80% by vol. methanol Ex. Solution Composition No. Used (parts by(Ex. No.) volume) 61 hexane fraction 0.70 80% by vol.

n-propanol 58 octane fraction 0.50 80% by vol.

n-propanol 59 octane fraction 80% by vol. i-propanol octane fraction 190% by vol.

methanol cyclopentane 0.50 by vol.

methanol entane ractlon toluene( 7:3)

B=22.72g =99.0% T= 0.20g 0.9%

16 9-16. B=0.11g T=0 1 90% by vol.

methanol hexane 64 fraction benzene 10: l

N= 0.01 g 0.1% 1-12 B=17.45g =99.0%

l 90% by vol.

methanol hexane 1 66 fraction benzene( 8:2)

N= 0.07g 04% 13-1790 =99.2% T= 0.07g 0.4%

B am -12.5% 1-8 2 1 by vol.

methanol hexane 65 fraction benzene( 8:2)

Table 7 -Continued Separation Stage B Separation of the neutralsubstances from the bitter substances Solvent phase Raffinate phaserecovered recovered Alcoholic-aqueous Solvent System No. of HC*solutionsolution Hydrocarbon phase Alcoholic phase extraccontent of content ofEx. Solution Composition Quan- Composition Quantion NS NS No. Used (pansby tity (mixture tity stages 7 BS BS (Ex.No.) volume) in l. with water)in 1. z x T y T hexane N= 281g =97.6% N= 0.01g 0.1% 93 67 fraction 1 70%by vol. 5.00 26 14-26 B= 0.07g 2.4% 1-13 B=16.42g =99.0%

benzene(8:2) methanol T= g 0 7o T= 0.16g 0.9%

hexane N= 5.52g =96.0% N= 0.05g 0.2% 94 68 fraction l 90% by vol. 0.9526 14-26 B= 0.23g 4.0% 113 B=26.92g =99.4%

benzene ethanol T= 0 g 0 T= 0.1 1g 0.4% :1)

hexane N= 494g =96.5% N= 0.22g 0.9% 95 69 fraction l 90% by vol. 1.27 2615-26 B= 018g 3.5% 1-14 B=23.84g =99.I% benzene(8:2) ethanol T= 0 g 0 T=0.01g 0.1%

hexane N= 5.16g =96.4% N= 004g 0.1% 96 fraction 1 by vol. 2.56 26 1426B=0.19g 3.6% 1-13 B 25.94g =98.9%

benzene(7:3) ethanol T= 0 g 0 T= 026g 1.0%

hexane N= 538g =99.6% N= 0.01g'= 0.1% 97 64 fraction 1 80% by vol. 4.0026 15-26 B= 0.02g =0.4% 1-13 B=28.29g '99.8%

benzene(6:4) ethanol T= 0 g O T= 0.04g 0.2%

Table 8 Separation Stage B Separation of the neutral substances from thebitter substances Solvent phase Rafiinate phase recovered recoveredAlcoholic-aqueous Solvent System No. of HC"-solution solutionHydrocarbon phase Alcoholic phase extraccontent of content of Ex.Solution Composition Quan- Composition Quantion NS NS No. Used (parts bytity (mixture tity stages B5 B5 (Ex.No.) volume) in l. with water) in I.z x T y T hexane I N= 4.15g =95. 1% N= 0.40g 1.5% 98 71 fraction 1 byvol. 3.70 31 18-31 B= 021g =4.9% 1-17 B=25.22g =98.%

t0luene(6:4) methanol T=0 g 0 T= 0.01g 0.1%

hexane N= 6.45g =99.2% N= 0.40g 1.5% 99 72 fraction 1 90% by vol. 5.00 858 B= 0.05g 0.8% 1-4 B=36.56g =99.9%

xylene(6:4) methanol T= 0 g 0 T= 0.05g 0.1%

hexane N= 8.57g =9s.5% N= 0.03,; 0.1% 100 73 fraction 1 80% by vol. 4.7626 14-26 B= 0.24g 1.5% 1-13 B=42.68g )9.2%

xylene(5:5) methanol T= 0 g 0 T= 0.3 lg 0.7%

heptane N= 4.06g =95.4% N= 0.02g 0.1% 101 76 fraction 1 932.2% by 1 1816 9-16 B= 0.17g =4.1% 1-8 B=27.92g =99.5%

benzene vol. methanol T= 0 g 0 T= 0.1 lg 0.4% 10:1

heptane N= 3.56g =96.4% N= 0.02g 0.1% 102 77 fraction 1 93.2% by 1 18 16B= 0.13g 3.6% 1-8 B=21.35g =99.5%

0991 16 lppgzlene vol. methanol T= 0 g O T= 0.0sg 0.4%

heptane N= 3.28g =89.2% N=0.07g 0.4% 103 75 fraction 0.5 93.2% by 0.6516 8-16 B= 040g =10.8% 1-9 B=19l64g =98.8%

benzene(8:2) vol. methanol T= 0 g 0 T= 0.16g 0.8%

heptane I N= 5.02g =77.5% N= 0.52g 2.1% 104 78 fraction 1 90% by vol.1.32 31 15-31 1.44g =2.23%- 117 B=24.73g =97.3%

bisgzlene ethanol T= 0 g 0 T= 0.17g 0.6% i

heptane N= .97g 6.5% N= 0. 10g 0.4% 105 79 fraction 1 90% by vol. 1.1026 l326 8 062g =13.5% 1-14 B=21.48g =99.3%

benzene ethanol T g 0 T= 0.06g 0.3% 10:1

heptane N= 1.69g =93.0% N= 0.01g 0.1% 106 82 fraction 0.5 80% by vol.2.5 26 1426 B= 0.04g 2.0% 1-13 B=10.18g =98.9%

methanol T= 0 g 0 T= 0.10g 1.0%

cyclopentane (5:5)

1. PROCESS FOR SUBSTANTIALLY SEPARATING THE ESSENTIAL INGREDIENTS OFHOPS, WHICH PROCESS COMPRISES SUBJECTING A PRIMARY EXTRACT OF HOPS IN ANORGANIC SOLVENT, CONTAINING AS COMPONENTS (I) NEUTRAL SUBSTANCES, (II)BITTER SUBSTANCES AND (III) TANNINS, TO A FIRST LIQUID-LIQUID EXTRACTIONWITH A SECOND ORGANIC SOLVENT DIFFERENT FROM SAID PRIMARY EXTRACTSOLVENT WHEREBY EITHER (III) THE TANNINS OR (I) THE NEUTRAL SUBSTANCESARE SUBSTANTIALLY SEPARATED OFF, LEAVING A RESIDUAL SOLUTION OF (I ANDII) NEUTRAL AND BITTER SUBSTANCES OR (III AND II) TANNINS AND BITTERSUBSTANCES, AND SUBJECTING THE RESIDUAL SOLUTION TO A SECONDLIQUID-LIQUID EXTRACTION WITH AN ORGANIC SOLVENT DIFFERENT FROM SAIDSECOND ORGANIC SOLVENT TO SEPARATE SAID SOLUTION INTO ITS COMPONENTS. 2.ProcEss as claimed in claim 1, wherein the primary extract solution is asolution of the hops ingredients in alcohol, alcohol containing water,benzene, alkyl benzenes or halogenated hydrocarbons.
 3. Process asclaimed in claim 1, wherein the primary extract solution is amethanolic-aqueous or an ethanolic-aqueous solution.
 4. Process asclaimed in claim 3, wherein the alcoholic primary extract solution has awater content of from about 5 to 30% by volume.
 5. Process as claimed inclaim 1, wherein the primary extract solution is a solution of the hopsingredients in benzene.
 6. Process as claimed in claim 1, wherein theprimary extract solution is a solution of the hops ingredients inmethylene chloride.
 7. Process as claimed in claim 1, wherein theprimary extract solution is subjected to the first liquid-liquidextraction in an extraction stage A, wherein the neutral and bittersubstances (i and ii) are separated from the tannins (iii), and to thesecond liquid-liquid extraction in an extraction B, wherein the neutralsubstances (i) are separated from the bitter substances (ii).
 8. Processas claimed in claim 7, wherein the primary extract solution is analcoholic solution and the primary extract solution is subjected, in theextraction stage A, to extraction with a hydrocarbon extractant 1comprising at least one of aliphatic hydrocarbons of from 5 to 10 carbonatoms, cyclo-aliphatic hydrocarbons of from 5 to 8 carbon atoms, andaromatic hydrocarbons selected from benzene and alkyl-substitutedbenzene derivatives, resulting in an extract of the neutral substancesand bitter substances (i and ii) in a hydrocarbon phase and leaving thetannins (iii) in an alcoholic phase; subjecting the extract from saidextraction stage A, containing (i and ii) in extraction stage B, toextraction with an alcohol extractant 2 comprising a mixture of at leastone lower aliphatic alcohol with water, to result in an extract of thebitter substances (ii) in an alcohol/water phase and leaving the neutralsubstances (i) in the hydrocarbon phase.
 9. Process as claimed in claim8, wherein the alcoholic primary extract solution contains water in suchamount that, in extraction stage A, the water content of the alcoholicphase amounts to between about 10 and 30% by volume and the aromatic andcycloaliphatic hydrocarbon content of extractant 1 amounts to betweenabout 10 and 60% by volume.
 10. Process as claimed in claim 8, whereinthe ratio by volume of extractant 1 to the alcoholic phase is in therange of from about 1 to
 10. 11. Process as claimed in claim 8, whereinthe hydrocarbon phase subjected to extraction in extraction stage B hasa cycloaliphatic and/or aromatic hydrocarbon content of less than about40% by volume, while the water content of extractant 2 is from about 10to 30 % by volume.
 12. Process as claimed in claim 8, wherein thehydrocarbon phase extracted in extraction stage B contains approximately0 to 30 % by volume of cycloaliphatic and/or aromatic hydrocarbons, andthe water content of extractant 2 is from about 10 to 20 % by volume.13. Process as claimed in claim 8, wherein the ratio by volume of saidhydrocarbon phase to extractant 2 is in the range of from about 0.1 to1.0.
 14. Process as claimed in claim 8, wherein the ratio by volume ofsaid hydrocarbon phase to the alcohol phase in extraction stage B isreduced to at least one half to one third of the corresponding ratio ofhydrocarbon phase to the alcoholic phase in extraction stage A. 15.Process as claimed in claim 8 wherein in extraction stage A theextractant is at least one halogenated hydrocarbon with from 1 to 3carbon atoms and with up to 3 halogen atoms.
 16. Process as claimed inclaim 7, wherein the primary extract solution is a solution of the hopsingredients in benzene, alkyl benzenes, or halogenated hydrocarbons, andthe primary extract solution is subjected, in extraction stage A, toextraction with an alcoholic extractant 1 comprising at least one ofaliphatic alcohols of from 1 to 3 carbon atoms, or mixtures of suchalcohols with water, whereby the neutral and bitter substances (i andii) remain in the hydrocarbon or halogenated hydrocarbon phase as araffinate, while the tannins (iii) are extracted into the alcoholicphase as a tannin extract; and subjecting, in extraction stage B, theraffinate from extraction stage A containing neutral and bittersubstances (i and ii), to extraction with an alcohol extractant 2comprising a mixture of lower aliphatic alcohol with water, to result inan extract of the bitter substances (ii) in an alcohol/water phase andleaving the neutral substances (i) in the hydrocarbon or halogenatedhydrocarbon phase.
 17. Process as claimed in claim 16, whereinmethanol-water mixtures containing from 10 to 40 % by volume of waterare used as extractant 1 in extraction stage A.
 18. Process as claimedin claim 16, wherein, in extraction stage A, the ratio by volume of thehydrocarbon phase to the alcoholic phase is in the range of from about 1to
 10. 19. Process as claimed in claim 16, wherein, in extraction stageA, the ratio by volume of the halogenated hydrocarbon phase to thealcoholic phase is in the range of from about 0.1 to
 2. 20. Process asclaimed in claim 16, wherein the hydrocarbon phase used in extractionstage B has an aromatic hydrocarbon content of less than about 40% byvolume, and the water content of extractant 2 is from about 10 to 30 %by volume.
 21. Process as claimed in claim 20, wherein the ratio byvolume of the hydrocarbon phase to extractant 2 is in the range of fromabout 0.1 to 1.0.
 22. Process as claimed in claim 16, wherein thehalogenated hydrocarbon phase used in extraction stage B is methylenechloride and extractant 2 is a methanol-water mixture containing from 30to 40% by volume of water.
 23. Process as claimed in claim 22, whereinthe ratio by volume of the halogenated hydrocarbon phase to extractant 2is in the range of from about 0.05 to 0.2.
 24. Process as claimed inclaim 1, wherein the neutral substances (i) are separated from thebitter substances and tannins (ii and iii) in the primary extractsolution in an extraction stage C, while the tannins (iii) are separatedfrom the bitter substances (ii) in an extraction stage D.
 25. Process asclaimed in claim 24, wherein the primary extract solution is analcoholic solution and the primary extract solution is subjected, inextraction stage C, to extraction with a hydrocarbon extractant 3comprising at least one of aliphatic hydrocarbons having from 5 to 10carbon atoms, cycloaliphatic hydrocarbons having from 5 to 8 carbonatoms, and aromatic hydrocarbons selected from benzene andalkylsubstituted benzene derivatives, to result in extraction of theneutral substances (i) into a hydrocarbon phase as a neutral substanceextract, while the bitter substances and tannins (ii) and (iii) are leftin an alcoholic phase; and the alcoholic phase left after extractionstage C is subjected, in extraction stage D, to extraction with ahydrocarbon extractant 4 comprising at least one of aliphatichydrocarbons of from 5 to 8 carbon atoms, aliphatic hydrocarbons of from5 to 10 carbon atoms, cycloaliphatic hydrocarbons of from 5 to 8 carbonatoms, and aromatic hydrocarbons selected from benzene andalkyl-substituted benzene derivatives, to result in extraction of thebitter substances (ii) into the hydrocarbon phase while the tannins(iii) are left in the alcoholic phase.
 26. Process as claimed in claim25, wherein the primary extract solution in extraction stage C has awater content of from about 5 to 30% by volume.
 27. Process as claimedin claim 25, wherein the ratio by volume of extractant 3 to thealcoholic phase is in the range of from 0.1 to
 1. 28. Process as claimedin claim 24, wherein the primary extract solution is a solution of thehops ingredients in benzene, alkylbenzenes or halogenated hydrocarbonsand the primary extract solution is subjected to, in extraction stage C,extraction with an alcoholic extractant 3 comprising at least one ofaliphatic alcohols of from 1 to 3 carbon atoms or mixtures of suchalcohols with water, to result in leaving the neutral substances (i) ina hydrocarbon or halogenated hydrocarbon phase while the tannins and thebitter substances (iii and ii) are extracted into the alcoholic phase;and the alcoholic extract phase from extraction stage C containingtannins and bitter substances (iii and ii) is subjected, in extractionstage D, to extraction with a hydrocarbon extractant 4 comprising atleast one of aliphatic hydrocarbons of from 5 to 10 carbon atoms,cycloaliphatic hydrocarbons having from 5 to 8 carbon atoms, andaromatic hydrocarbons selected from benzene and alkyl-substitutedbenzene derivatives, to result in extraction of the bitter substances(ii) into the hydrocarbon phase while the tannins (iii) remain in thealcoholic phase.
 29. Process as claimed in claim 28, wherein amethanol-water mixture containing from 10 to 40% by volume of water isused as extractant 3 in extraction stage C.
 30. Process as claimed inclaim 28, wherein the primary extract solution is a solution containinga halogenated hydrocarbon and the ratio by volume of the halogenatedhydrocarbon phase to the alcoholic phase is in the range of from 0.1 to0.4.
 31. Process as claimed in claim 28, wherein the alcoholic phaseused in extraction stage D has a water content of from about 10 to 40%by volume, and the hydrocarbon phase used as extractant 4 has anaromatic hydrocarbon content of from about 0 to 90 % by volume. 32.Process as claimed in claim 28, wherein the ratio by volume ofextractant 4 to the alcoholic phase is in the range of from about 1 to10.
 33. Process as claimed in claim 28, wherein the ratio by volume ofthe hydrocarbon phase to the alcoholic phase in extraction stage D isincreased by at least about 5 to 20 times in relation to thecorresponding ratio in extraction stage C.